Analytische Chemie
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Sixteen Ayyubid-Mamluk glazed pottery sherds were analyzed in order to identify and characterize the elemental composition to determine their provenance. The tested sherds were collected from the historical site of Karak Castle, southern Jordan.
Chemical analysis for the sixteen samples has been carried out using Synchrotron Radiation X-ray Fluorescence Spectrometry (SR-XRF) Technique. Furthermore, the semiquantitative analysis of the elements Fe – Cu – Zn – Br – Rb – Sr – Y – Zr – Nb – Mo – Pd – Ag – Cd and Pb has been performed for the samples based on Principal Component Analysis (PCA) and hierarchical Cluster Analysis with Bray-Curtis in order to define grouping of different glazed pottery by obtaining information on their similarity and clustering. The results of chemical analysis provided persuasive evidence that the Karak Castle pottery sherds have at least three different sources of provenance.
Zn is known to be located in the reactive centers of various enzymes, which play a major role in the mineralization process at sites where new bone formation occurs. In addition, elevated Zn levels are supposed to increase the proliferation rate of osteoblasts [1] and may lead to a stimulation of bone formation in vitro and in vivo [2]. Consequently, Zn seems to play an essential role in bone formation and mineralization through various pathways. We thus expected Zn levels to be altered at sites of extensive bone formation like in the case of fracture healing.
We measured the same areas on human bone samples with both a scanning confocal synchrotron radiation induced micro X-ray fluorescence (SR-μXRF) at the FLUO beamline (ANKA) and a full-field Color X-ray Camera at the BAMline (Bessy II) setup in order to find the ideal SR-μXRF imaging method to investigate trace element distributions in bone samples. As zinc is a trace element of special interest in bone, the setups were optimized for Zn detection. The setups were compared concerning count rate, required measurement time and resolution. We could show that the ideal method is depending on the element of interest. While for Ca (a major constituent of the bone with a low energy of 3.69keV for K) the Color X-ray Camera provided us with a higher resolution in the plane, for Zn (a trace element in bone) only the confocal SR-μXRF was able to sufficiently image the distribution.
Biopsies of healing osteoporotic fractures (Vertebral compression fractures (VCFs)) were investigated in regard to their Zn distribution. The samples were measured with a confocal SR-μXRF setup with a 10 μm x 15 μm resolution at the FLUO beamline at ANKA. As we found increased Zn levels, which seemed to be accumulated in narrow structures between bone packages we also investigated thin cuts (4 μm thick) of two sample areas with a higher resolution of 1 μm x 1 μm (monochromatic beam with E= 17 keV) at B16 at Diamond SR facility.
We will present the advantages and disadvantages of all three SR-μXRF setups (ANKA FLUO beamline, Bessy II BAMline, and Diamond B16) for imaging elemental distributions in bone with a focus on Zn. We will also show the distribution of Zn in healing VCFs.
Fire-gilding or amalgam gilding is a historical technique for the gilding of objects. The object to be gilded is coated with an amalgam (a solution of gold (Au) in mercury (Hg)). By heating, the largest part of the Hg is subsequently evaporated and there remains a gold layer, containing still detectable amounts of Hg.
The information on the used gilding technique might be crucial for the conservation and preservation of archaeological objects. Therefore, the main objective of this work is the detailed understanding of the behaviour of Hg under conditions of fire gilding. I.e. the understanding of the diffusion and evaporating behaviour of Hg, depending on parameters like substrate material (silver, copper, bronze, brass...), heating temperature and duration, and the resulting Hg depth profiles under these conditions. Secondary objective is the establishment of a measurement protocol for the unambiguous identification of different types of gilding, based solely on non-destructive methods, which can be applied to historical samples.
In a first step, fire-gilded samples have been prepared on Cu and Ag sheet metal, respectively. Some of the gildings were produced by a professional goldsmith; another set of samples was produced under laboratory conditions. These samples have been examined with NAA (neutron activation analysis) and SR-XRF (synchrotron radiation induced X-ray fluorescence). First results of these measurements will be presented and discussed.
Fire-gilding or amalgam gilding is a historical technique for the gilding of objects. The object to be gilded is coated with an amalgam (a solution of gold (Au) in mercury (Hg)). By heating, the largest part of the Hg is subsequently evaporated and there remains a gold layer, containing still detectable amounts of Hg.
The information on the used gilding technique might be crucial for the conservation and preservation of archaeological objects. Therefore, the main objective of this work is the detailed understanding of the behaviour of Hg under conditions of fire gilding. I.e. the understanding of the diffusion and evaporating behaviour of Hg, depending on parameters like substrate material (silver, copper, bronze, brass...), heating temperature and duration, and the resulting Hg depth profiles under these conditions. Secondary objective is the establishment of a measurement protocol for the unambiguous identification of different types of gilding, based solely on non-destructive methods, which can be applied to historical samples.
In a first step, fire-gilded samples have been prepared on Cu and Ag sheet metal, respectively. Some of the gildings were produced by a professional goldsmith; another set of samples was produced under laboratory conditions. These samples have been examined with NAA (neutron activation analysis) and SR-XRF (synchrotron radiation induced X-ray fluorescence). First results of these measurements will be presented and discussed.
Gold ist eines der sieben schon im Altertum bekannten Metalle und wurde wg. seines Glanzes und seiner Seltenheit von alters her als Tauschmittel und zur Herstellung von Schmuck benutzt. Außerdem ist es einfach bearbeitbar und weitestgehend gegen chemische Einflüsse resistent.
Die Untersuchungen von Gold mit synchrotronstrahlungsangeregter Röntgenfluoreszenzanalyse sind zerstörungsfrei und geben Auskunft über die in der untersuchten Probe vorhandenen chemischen Elemente.
Bei den hier vorgestellten Untersuchungen an der BAMline stehen Fragestellungen wie Herkunft, Herstellungsverfahren und Zusammengehörigkeit von Goldfunden im Vordergrund. Die verschiedenen Fragestellungen werden an einer Reihe von Beispielen erläutert die vom Wikingerschatz aus Hiddensee über die Himmelsscheibe von Nebra bis hin zu Funden aus Ägypten langen. Zusätzlich werden die modernen Messmethoden vorgestellt, die am Synchrotron heutzutage zur Verfügung stehen.
Gold ist eines der sieben schon im Altertum bekannten Metalle und wurde wg. seines Glanzes und seiner Seltenheit von alters her als Tauschmittel und zur Herstellung von Schmuck benutzt. Außerdem ist es einfach bearbeitbar und weitestgehend gegen chemische Einflüsse resistent.
Die Untersuchungen von Gold mit synchrotronstrahlungsangeregter Röntgenfluoreszenzanalyse sind zerstörungsfrei und geben Auskunft über die in der untersuchten Probe vorhandenen chemischen Elemente.
Bei den hier vorgestellten Untersuchungen an der BAMline stehen Fragestellungen wie Herkunft, Herstellungsverfahren und Zusammengehörigkeit von Goldfunden im Vordergrund. Die verschiedenen Fragestellungen werden an einer Reihe von Beispielen erläutert die vom Wikingerschatz aus Hiddensee über die Himmelsscheibe von Nebra bis hin zu Funden aus Ägypten langen. Zusätzlich werden die modernen Messmethoden vorgestellt, die am Synchrotron heutzutage zur Verfügung stehen.
The Color X-ray Camera CXC or SLcam® is an energy-resolving X-ray camera capable of energy- and space-resolved measurements. It consists of a high-speed CCD detector coupled to a polycapil-lary optic that conducts the X-ray photons from the probe to distinct pixels onto the detector.
The camera is capable of fast acquisition of spatially and energy resolved fluorescence images. A dedicated software enables the acquisition and the online processing of the spectral data for all 69696 pixels, leading to a real-time visualization of the elements distribution in a sample. It was developed in a joint project with BAM, IFG Berlin and PN Sensors.
In this contribution we will mainly discuss the use of the CXC at our beamline, the BAMline at BESSY II and imaging applications of the CXC from different areas, like biology and archaeometry. Additionally new developments for the use of the detector without optics, like wavelength dispersive detection or 1shot-XANES, will be presented.
Tattooing practice is adopted worldwide and represents a socio-cultural phenomenon, but the injection into the skin of coloring agents, such as metals might pose a serious health problem. Tattoo ink compounds are in general not officially controlled. Moreover, the origins as well as the chemical and toxicological specifications of these coloring agents are hardly known by the producers, the tattooists and by the consumers. In this view, the aim of this study was to characterize the metal composition of tattoo inks available in the market and to draw attention to the associated risk for human health.
A set of tattoo inks from the brand Kuro Sumi was analyzed by means of Synchrotron-based X-ray Fluorescence spectrometry (Sy-XRF) at BAMline @ BESSY II and Raman Spectroscopy using the XploRA confocal Raman microscope (785 nm laser) at the LIBPhys-UNL. Carbon black, rutile, phtalo blue, phtalo green, helizarin red, helizarin yellow and dioxazine violet were respectively identified in black, white, blue, green, red, yellow and violet inks. However, a wide range of transition and heavy metals, potentially hazardous was revealed by Sy-XRF. A semi-quantitative evaluation has revealed, in some inks, amounts of Cr, Cu, Zn and Pb higher than the allowed according to the resolution adopted by the Council of Europe on the safety of tattoos and permanent make-up.
Toxic metals in tattoo inks
(2016)
Tattooing practice is adopted worldwide and represents a socio-cultural phenomenon, but the injection into the skin of coloring agents, such as metals might pose a serious health problem. Tattoo ink compounds are in general not officially controlled. Moreover, the origins as well as the chemical and toxicological specifications of these coloring agents are hardly known by the producers, the tattooists and by the consumers. In this view, the aim of this study was to characterize the metal composition of tattoo inks available in the market and to draw attention to the associated risk for human health.
A set of tattoo inks from the brand Kuro Sumi was analyzed by means of Synchrotron-based X-ray Fluorescence spectrometry (Sy-XRF) at BAMline @ BESSY II and Raman Spectroscopy using the XploRA confocal Raman microscope (785 nm laser). Carbon black, rutile, phtalo blue, phtalo green, helizarin red, helizarin yellow and dioxazine violet were respectively identified in black, white, blue, green, red, yellow and violet inks. However, a wide range of transition and heavy metals, potentially hazardous was revealed by Sy-XRF. A semi-quantitative evaluation has revealed, in some inks, amounts of Cr, Cu, Zn and Pb higher than the allowed according to the resolution adopted by the Council of Europe on the safety of tattoos and permanent make-up (PMU.
The newly developed EXAFS set-up comprises both time- and spatially-resolved EXAFS information simultaneously in a single-shot. This facile, stable and scanningless set-up was tested at the BAMline @ BESSY-II (Berlin, Germany). The primary broadband beam is generated by a filter/X-ray-mirror combination (bandpass). The transmitted beam through the sample is diffracted by a convexly bent Si (111) crystal, producing a divergent beam. This, in turn, is collected by an area sensitive detector based on a CCD camera, in a theta - 2 theta geometry.
The first in situ measurements were successfully carried out and hereby presented. The case-study involved a well known reaction, in which structural changes are induced over time, and continuously measured. We were able to track structural changes within a 1s time resolution.
Gold mosaics, made from gold and glass, are one of the best expressions of Late Antique Byzantine and Early Islamic art. The gold alloys, whose composition seems to indicate that gold coins were re-used to fabricate the tesserae, can be used to provide information on the mosaics chronology. Monetary Byzantine gold is in fact characterized by the presence of Pt, which contents in the gold alloy change over time, but Pt must be measured in 0.2-0.4 µm thickness gold leaves that were beaten to be sandwiched between two glass layers.
To analyze this samples the D²XRF set-up at the BAMline at the BESSY synchrotron in Berlin was used. The combination of a crystal for wavelength dispersion and an energy resolving single photon counting pnCCD allows the realization of this very simple wavelength dispersive detection system. With this system an MDL of 1 μg/g for the determination of Pt in Au under optimal conditions can be reached.
Gold leaf tesserae from nine archaeological sites, covering the period that goes from the 5th c. to the 8th c., were analyzed. The presence of Pt in the majority of the samples confirmed the re-use of coins. The Pt contents separate the samples in three groups, one of which having the same chemical characteristics as the Byzantine gold could be compared to dated coins for chronology. The higher Pt contents for one of other groups suggest
Die Mitte des 16. Jahrhunderts gegründete Dresdener Goldschmiedeinnung, geriet im 19. Jahrhundert in wirtschaftliche Schwierigkeiten, was letztendlich zu ihrer Auflösung führte. Im Zuge dessen wurde 1872 auch der historische Innungspokal für 80 Taler an das Grüne Gewölbe in Dresden verkauft. Sowohl das Empfehlungsschreiben des damaligen Direktors als auch die Zustimmung zum zügigen Ankauf dürften Beleg dafür sein, dass man damals der festen Überzeugung war, ein etwa 250 Jahre altes, authentisches Silbergefäß erworben zu haben. Die aktuelle kunstwissenschaftliche Begutachtung des Innungspokals lässt begründete Fragen zum Alter und zur Originalität des Objektes, welches heute in der Sammlung des Grünen Gewölbes präsentiert wird, aufkommen. Die kunst-wissenschaftliche und kunsttechnologische Expertise reicht hier allein ftir eine gesicherte Altersbestimmung nicht aus und soll deshalb durch naturwissenschaftliche Untersuchungen zur Materialzusammensetzung unterstützt werden.
Wilson´s disease, a rare genetic disorder of the copper metabolism, causes the copper accumulation in various organs, leading to manifold hepatic, neurological and psychiatric symptoms. To study the elemental distribution, human Wilson´s disease liver samples were analyzed by means of LA-ICP-MS. Results demonstrated an inhomogeneous copper and iron distribution in human liver with hotspots of very high intensities. Both elements were quantified by an external calibration using matrix-matched standards made of gelatin, showing concentrations up to several thousand micrograms per gram. Additionally, results were validated by means of synchrotron radiation based μXRF at the BAMline at BESSYII (Helmholtz-Zentrum Berlin).
Wilson´s disease (WD) is a rare genetic disorder of the copper metabolism, causing the accumulation of copper in different organs, including the liver, the central nervous system and cornea. This way, WD initiates manifold hepatic, neurological or psychiatric symptoms. To learn about the elemental distribution and present species in WD, liver samples were analyzed by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), micro X-ray fluorescence (μXRF) and X-ray absorption near edge structure spectroscopy (XANES).
Within this work, LA-ICP-MS was applied to study the distribution of copper and iron in human liver samples, which were collected by a liver biopsy of WD and control patients within a medical investigation. The analysis by LA-ICP-MS was performed with a 213 nm Nd:YAG laser using a spatial resolution of 10 μm and a scan rate of 20 μm/s. In a next step, copper and iron were quantified by LA-ICP-MS using homemade matrix-matched standards made of gelatin. Results showed an inhomogeneous copper and iron distribution in human liver with hotspots up to several thousand micrograms per gram liver within the hepatocytes.
Additionally, results for the elemental distribution in WD were validated by means of synchrotron radiation-based μXRF with a beam size of 4 μm at the BAMline at BESSYII (Helmholtz-Zentrum Berlin). Furthermore, XANES was performed to identify the present oxidation states of copper in WD, indicating a mixture of copper(I) and copper(II) within the liver tissue.
In the contemporary medicine, rhodanine staining is routinely used to determine the copper distribution in liver tissues. Nevertheless, this method does not provide results with a high sensitivity in comparison to LA-ICP-MS. Therefore, the presented LA-ICP-MS method offers a new possible diagnostic tool. These results may also contribute to a better understanding of Wilson´s disease and its development.
Airborne particulate matter is an issue of growing concern in industrialized countries.
Particles with diameters of less than 10 μm, in particular those with less 2.5 μm, are of special
concern, as they can enter the human lungs and contribute to various cardiovascular and
respiratory diseases. As the composition and health effects of airborne particles in urban, rural
and industrial outdoor air has been studied abundantly, our focus lies on the analysis of
airborne particle samples collected indoors, which may also have a significant effect on
human health, depending on the chemical composition of the particles and the chemical
bonding state, in which elements are present. This chemical speciation can be obtained using
X-ray absorption near edge structure (XANES) analysis, which requires a tunable excitation
source and therefore has to be carried out at synchrotron facilities. For this work, samples
were collected in office rooms of the Atominstitut building.
The BAMline at BESSYII, Berlin, features a double-multilayer monochromator (DMM) and a
double-crystal monochromator (DCM). The DCM offers an energy resolution E/ΔE of around
103, which makes it suitable for X-ray absorption fine structure (XAFS) applications. The
Atominstitut SR-TXRF vacuum chamber, formerly located at HASYLAB, Beamline L, is
now available at the BAMline. The chamber offers a sample changer for up to 8 quartz
carriers suitable for total reflection X-ray fluorescence analysis (TXRF) and was equipped
with a 30 mm² silicon drift detector (SDD). Aerosol samples were produced using a modified
three-stage Dekati™ impactor. For this work, only the coarse (2.5 to 10 μm, Stage 2) and the
fine particle fraction (1 to 2.5 μm, Stage 3), were of interest. XANES analysis was performed
for the elements Cr, Cu and Zn. Oxidation states of these 3 elements will be presented.
The X-ray Fluorescence beamline at ELETTRA operates in partnership with the IAEA an
ultra-high vacuum instrument with a 7-axis manipulator suitable for a variety of X-ray
analytical techniques, such as grazing incidence X-ray fluorescence analysis (GI-XRF),
TXRF, X-ray reflectometry (XRR) and XANES. Samples were produced using a four-stage
Sioutas Personal Cascade Impactor. With this impactor, it is possible to produce sizefractionated
samples down to the sub-μm range (Stages: A > 2.5 μm, B 1 to 2.5 μm, C 0.5 to
1 μm and D 0.25 to 0.5 μm). Direct sampling was performed on siliconized 25 mm Si wafers
suitable for TXRF. Cu-K edge SR-TXRF-XANES analysis was carried out for samples of all
impactor stages. Results of these experiments will be shown.
Airborne particulate matter is an issue of growing concern in industrialized countries. Particles with diameters of less than 10 μm (especially those smaller than 2.5 μm) can enter the human respiratory system and contribute to various diseases depending on their chemical composition and the chemical bonding state, in which elements are present. This chemical speciation can be obtained using X-ray absorption near-edge structure analysis (XANES), which requires a tunable excitation source and therefore has to be carried out at synchrotron facilities. Our special interest lies on the analysis of indoor airborne particulate matter, as particle composition and health effects of outdoor particles have been studied abundantly. For this work, samples were collected in various office rooms in the Atominstitut (ATI) building.
The BAMline at BESSYII features a double-multilayer monochromator (DMM) and a double-crystal monochromator (DCM). The DCM offers an energy resolution E/ΔE of around 103, which makes it suitable for XANES applications. The ATI SR-TXRF vacuum chamber, formerly located at HASYLAB, Beamline L, is now available at the BAMline. The chamber offers a sample changer for up to 8 quartz reflectors and a 30 mm² silicon drift detector (SDD) was used. Aerosol samples were produced using a modified three-stage Dekati™ impactor. For this work, only the coarse (2.5 to 10 μm) and the fine particle fraction (1 to 2.5 μm), were of interest. XANES results of Cr, Cu and Zn will be presented on this poster.
The X-ray Fluorescence beamline at ELETTRA operates in partnership with the IAEA an ultra-high vacuum instrument with a 7-axis manipulator suitable for a variety of X-ray analytical techniques, such as grazing incidence and total reflection X-ray fluorescence analysis (GI-XRF and TXRF), X-ray reflectometry (XRR) and XANES. Samples were produced using a four-stage Sioutas Personal Cascade Impactor. With this impactor, it is possible to produce size-fractionated samples down to the sub-μm range (Stages: A > 2.5 μm, B 1 to 2.5 μm, C 0.5 to 1 μm and D 0.25 to 0.5 μm). Direct sampling was performed on siliconized 25 mm Si wafers suitable for TXRF. Cu-K edge SR-TXRF-XANES analysis was carried out for samples of all impactor stages. Results of these experiments will be shown.
High Speed, High Resolution imaging spectrometers based on pnCCDs for XRF and XRD applications
(2016)
For many years pnCCDs have been well known as X-ray detectors for spectroscopic imaging in many fields of science: X-Ray Fluorescence analysis (XRF), X-ray Diffraction (XRD) with light sources in large accelerator facilities as well as with laboratory light sources or with X-rays from celestial sources in X-ray astronomy. A brief introduction in GEXRF (Grazing Emission XRF) measurements with a laboratory laser produced plasma source will be given, PIXE (Particle Induced X-ray Emission) measurements and D2XRF (Double Dispersive X-Ray Fluorescence) and Slicing experiments with pnCCDs coupled to polycapillary optics performed at the BESSY synchrotron will be shown. Energy-dispersive Laue diffraction with ultra-hard X-rays for the analysis of defects in metals will conclude the overview of spectroscopic X-ray imaging measurements in the field of structure and dynamics of matter.
High Speed X-ray Imaging and Spectroscopy with pnCCDs: XRF, XRD and PIXE measurements (and others)
(2016)
For many years pnCCDs have been well known as X-ray detectors for spectroscopic imaging in
many fields of science: X-Ray Fluorescence analysis (XRF), X-ray Diffraction (XRD) with light
sources in large accelerator facilities as well as with laboratory light sources or with X-rays from
celestial sources in X-ray astronomy. A brief introduction in GEXRF (Grazing Emission XRF)
measurements with a laboratory laser produced plasma source will be given, PIXE (Particle Induced
X-ray Emission) measurements and D2XRF (Double Dispersive X-Ray Fluorescence) and Slicing
experiments with pnCCDs coupled to polycapillary optics performed at the BESSY synchrotron will
be shown. Energy-dispersive Laue diffraction with ultra-hard X-rays for the analysis of defects
in metals will conclude the overview of spectroscopic X-ray imaging measurements in the field of
structure and dynamics of matter.
In this study a metal-matrix-composite with aluminum matrix and Al2O3 particles was investigated with x-ray refraction topography and in-situ tensile loading. It could be observed that after reaching a certain load the specific surface increased steadily. However, the classical radiographs taken for comparison show no damage in the sample.
Time-resolved in situ investigation of Portland cement hydration influenced by chemical admixtures
(2016)
Numerous admixtures are used in the building practice to customize the properties of the cement paste during application. The influences of admixtures on the course of cement hydration and formation of hydrate phases have to be considered. Polycarboxylate ether (PCE) based polymeric superplasticizers (SPs) are known to retard the setting of the cement paste. The extent of the retardation differs depending on the molecular structure of the SP. Additionally, the presence of a stabilizing agent (SA) in the cement paste has a retarding side effect on the setting. The initial cement hydration processes and the detailed mechanisms of the retardation influenced by PCEs, as well as their interactions with particular SAs, are insufficiently understood. Up to now, only the results of phenomenological studies were taken into account to describe this retardation process. A detailed structure analysis monitoring the change of the phase composition during the hydration was never applied. Both SP and SA affect the adsorption of the sulphate ions on the clinker particles, causing changes in the formation of ettringite during the initial hydration, and are therefore a crucial part of the setting process itself. Here, the initial hydration of cement influenced by the interaction of SP and SA was monitored in situ by synchrotron X-ray diffraction. The high time resolution of the measurements allowed a continuous detection of the hydrates formed. The hydration was followed from the starting point of water addition and for couple of hours afterwards. The hydration of the levitated cement pellets containing starch as SA was initialized by adding aqueous solutions of different commercial SPs. Changes in the ettringite formation were detected in comparison to the reference hydration of pure cement.
Synchrotron-radiation enables the adjustment of the XPS information depth and, thus, the visualization of depth profiles of the elemental composition within the first 10 nm of a surface. This project deals with the analysis of core-shell nanoparticles. It constitutes first steps towards a valid methodology for studying the surface chemistry of nanoparticles in a quantitative and accurate manner.
The gold finds from Bernstorf, in the Freising district of Bavaria, were discovered in 1998, in the area of a Bronze Age settlement. First analyses with X-ray fluorescence (XRF) revealed gold of an unusually high purity grade, which was explained by using cementation techniques.
A newer analysis with laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) indicated an even higher purity. These analytical results were the starting point of an ongoing discussion. The amount and type of the detected contaminants were highly controversial and led to contradictory interpretations.
We reanalysed 11 gold samples with synchrotron radiation induced X-ray fluorescence (SRXRF) at the BAMline at BESSY-II. To reach the desired detection limits a thorough analysis with three different excitation energies and detection conditions were applied to confirm or disprove the previous results.
In this contribution we will get into the details for the need of the different measurement conditions and the virtues of the use of synchrotron radiation. The use and effectiveness of cementation techniques will be addressed. Finally we will present the achieved results and their impact on the discussion.
The BAMline at the synchrotron BESSY II in Berlin supplies users with up to date analytical x-ray methods for the energy range between 5 and 50 keV. Additional to XRF with micron Resolution it provides amongst other things the possibility to use TXRF and XANES. Especially the use of
the so-called Color X-Ray Camera (CXC) opens the possibility to use new and effective detection schemes, which allow to measure simultaneously distributions of elements or Absorption spectra in a motionless mode.
In this talk the analytical possibilities at the BAMline for samples with biological Background will be introduced. The available methods will be presented and discussed for various examples.
A perspective for the future use for XANES in grazing emission and TXRF geometries for plant materials will be given.
Die Eigenschaften und die Verlässlichkeit von Materialien jeglicher Art sind seit jeher die Grundlagen der Technik einer Gesellschaft. Tiefgreifende Kenntnisse über sie sind deshalb eine Voraussetzung um neue Produkte zu entwickeln, Verlässlichkeit zu gewährleisten, oder aber auch, wie in der Archäometrie, Kenntnisse über die Vergangenheit zu gewinnen. Ein Schlüssel zum Verständnis ist das Wissen über die chemische Zusammensetzung und die Struktur von Materialien Die Analyse mit Synchrotronstrahlung bietet hierfür herausragende Werkzeuge an, die zerstörungsfrei und hochsensitiv sind. Mit Röntgenfluoreszenzanalyse kann die elementare Zusammensetzung in winzigen Proben bis auf μg/g bestimmt werden. Anwendungsbeispiele aus verschiedenen Themengebieten, aber besonders von archäologischen Fragestellungen wie z.B. dem Goldfund von Bernstorf werden im Vortrag vorgestellt.
News from the BAMline
(2017)
Airborne particulate matter is a topic of growing interest. Particles with aerodynamic diameters less than 10 μm (PM 10) and especially the fine fraction below 2.5 μm (PM2.5) are of particular importance, as they can enter the human respiratory system and cause acute and
chronic respiratory or cardiovascular diseases. The mass distribution of airborne particles in dependence of their diameters is well-known, but also the abundance and temporal variation of trace elements in air (mass concentrations down to the pg/m³ range) are crucial.
These elements originate from various natural (abrasion, erosion) and anthropogenic sources (combustion, road traffic), which complicate the discrimination between harmless and toxic emissions. Some new methods of investigation are therefore needed and X-ray fluorescence spectroscopy has ascertained ist huge potential in this matter, thanks to the possibility to determine simultaneously, in a time-resolved manner, the mass concentrations of critical elements which can be considered as markers of a potential toxic source. A method for the quantitative Analysis of airborne particles directly collected on sample substrates (30 mm quartz reflectors and 1" Si wafers suited for total-reflection X-ray fluorescence analysis (TXRF) will be presented.
Samplings were performed using a three- stage Dekati™ PM10 impactor (>10 μm, 2.5 to 10 μm and 1 to 2.5 μm) and a four-stage Sioutas Personal Cascade Impactor (>2.5 μm, 1 to 2.5 μm,0.5 to 1 μm and 0.25 to 0.5 μm) at indoor and outdoor sites at the Atominstitut (Vienna, Austria). Quantitative results of two outdoor test sampling campaigns (July 2016 and January 2017) will be presented and discussed. Low detection limits were assessed via TXRF and range from several 10 to several 100 pg/m³ depending on the element and particle size fraction.
Ein Konvolut einzelner Schmuckstücke und die Goldbeigaben eines angeblichen Grabfundes wurden technologisch und analytisch untersucht. Die meisten Objekte sind Blecharbeiten, die aus einer Vielzahl von Einzelteilen mit metallischem Goldlot zusammengefügt und mit Granulation oder granulations-imitierendem Perl- oder Kerbdraht verziert wurden. Nur vier kleine Ohrringe sind massiv gegossen.
Zwei Zierbleche dürften über Patrizen (Positivmodeln), die Deckel der Astragale in Matrizen (Negativmodeln) geformt worden sein. Alle Objekte wurden mit Synchrotron- und atmosphärischer Röntgenfluoreszenz analysiert. Die Daten zeigen das breite Spektrum an Goldlegierungen, die im 7./6. Jahrhundert v. Chr. in Kleinasien verarbeitet wurden: vom natürlichen Seifengold (Elektrum) bis zu geläutertem, fast reinem Gold. Eine Korrelation zwischen Goldqualität und Verarbeitungsmethode konnte nicht festgestellt werden. Sowohl hochreines als auch mit viel Silber und Kupfer legiertes Gold wurde zum Schmieden von Blecharbeiten, aber auch zum Massivguss verwendet. Aus der Goldfarbe kann wegen des Phänomens der oberflächlichen Goldanreicherung nicht auf eine Legierungszusammensetzung geschlossen werden. Der 1963 angekaufte Fundkomplex aus lydischen Metallarbeiten und ostionischen Salbgefäßen aus Ton dürfte einen Grabfund des frühen 6. Jahrhunderts v. Chr. darstellen, dessen Herkunft aus Ephesos jedoch nicht zu sichern ist.
In the quest for finding the ideal synchrotron-radiation-induced imaging method for the investigation of trace element distributions in human bone samples, experiments were performed using both a scanning confocal synchrotron radiation micro X-ray fluorescence (SR-mXRF) (FLUO beamline at ANKA) setup and a full-field color X-ray camera (BAMline at BESSY-II) setup. As zinc is a trace element of special interest in bone, the setups were optimized for its detection. The setups were compared with respect to count rate, required measurement time and spatial resolution. It was demonstrated that the ideal method depends on the element of interest. Although for Ca (a major constituent of the bone with a low energy of 3.69 keV for its K alpha XRF line) the color X-ray camera provided a higher resolution in the plane, for Zn (a trace element in bone) only the confocal SR-µXRF setup was able to sufficiently image the distribution.
The gold finds from Bernstorf, in the Freising district of Bavaria, were discovered in 1998, in the area of a Bronze Age settlement. First analyses with X-ray fluorescence (XRF) revealed gold of an unusually high purity grade, which was explained by the use of cementation techniques. A newer analysis with laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) indicated an even higher purity. The analytical results were the starting point of an ongoing discussion. In this study, we re-analysed 11 gold samples with Synchrotron radiation–induced X-ray fluorescence at the BAMline at BESSY. In a thorough analysis, different excitation and detection conditions were applied to confirm or disprove the previous results. It was shown that the purity of the gold from the specimen is higher than 99.9%. The main impurities are silver in a range between 20 and 200 μg/g and copper between 1 and 10 μg/g. The results are in very good agreement with the LA–ICP–MS measurements and provide basic information for discussions about provenance, processing techniques or considerations of authenticity.
Absorptionskantentomographie, auch bekannt als differentielle Tomographie an Kanten, ist ein Verfahren, bei dem ausgenutzt wird, dass sich die Schwächung von Röntgenstrahlen beim Übergang der Photonenenergie über die Absorptionskanten sprunghaft ändert. Die Verwendung von Synchrotronstrahlung ermöglicht die Anwendung der Absorptionskantentomographie für nahezu jedes Element, da sie eine intensive, durchstimmbare Strahlenquelle mit kleiner Bandbreite darstellt. Der Mikrotomographieaufbau der BAM am Elektronenspeicherring BESSY II eignet sich mit einem Energiebereich von 5 keV bis über 60 keV und einer Ortsauflösung besser als 0.5 µm zur differentiellen Tomographie an den K-Kanten der Elemente von Chrom bis zu den Lanthaniden, bei Einbeziehung der L-Kante bis zu Uran.
In dieser Arbeit wird die Absorptionskantentomographie ausgenutzt, um das Gefüge von Legierungen dreidimensional und nichtdestruktiv zu vermessen. Als Beispiel wird eine Legierung zwischen Magnesium, Yttrium und Zink analysiert, die sich gegenüber unlegiertem Magnesium durch größere Festigkeit und geringere Korrosionsanfälligkeit auszeichnet. Der Grund dafür liegt in der Bildung einer kristallographisch hochgeordneten Phase (long period stacking ordered - LPSO) der Legierungsbestandteile, die die Matrix in Form von Fasern durchzieht. Anhand ihres Yttriumgehaltes wird die dreidimensionale Verteilung der LPSO-Phase in der Matrix für verschiedene Proben bestimmt und mit Schnittbildern und Korrosionstests verglichen. Die Absorptionskantentomographie erweist sich als eine geeignete Methode, um die dreidimensionale Mikrostruktur von Legierungen zu charakterisieren.
Absorptionskantentomographie, auch bekannt als differentielle Tomographie an Kanten, ist ein Verfahren, bei dem ausgenutzt wird, dass sich die Schwächung von Röntgenstrahlen beim Übergang der Photonenenergie über die Absorptionskanten sprunghaft ändert. Die Verwendung von Synchrotronstrahlung ermöglicht die Anwendung der Absorptionskantentomographie für nahezu jedes Element, da sie eine intensive, durchstimmbare Strahlenquelle mit kleiner Bandbreite darstellt. Der Mikrotomographieaufbau der BAM am Elektronenspeicherring BESSY II eignet sich mit einem Energiebereich von 5 keV bis über 60 keV und einer Ortsauflösung besser als 0.5 µm zur differentiellen Tomographie an den K-Kanten der Elemente von Chrom bis zu den Lanthaniden, bei Einbeziehung der L-Kante bis zu Uran.
In dieser Arbeit wird die Absorptionskantentomographie ausgenutzt, um das Gefüge von Legierungen dreidimensional und nichtdestruktiv zu vermessen. Als Beispiel wird eine Legierung zwischen Magnesium, Yttrium und Zink analysiert, die sich gegenüber unlegiertem Magnesium durch größere Festigkeit und geringere Korrosionsanfälligkeit auszeichnet. Der Grund dafür liegt in der Bildung einer kristallographisch hochgeordneten Phase (long period stacking ordered - LPSO) der Legierungsbestandteile, die die Matrix in Form von Fasern durchzieht. Anhand ihres Yttriumgehaltes wird die dreidimensionale Verteilung der LPSO-Phase in der Matrix für verschiedene Proben bestimmt und mit Schnittbildern und Korrosionstests verglichen. Die Absorptionskantentomographie erweist sich als eine geeignete Methode, um die dreidimensionale Mikrostruktur von Legierungen zu charakterisieren.
Mechanaochemistry is an effecthive method to yield pure compounds within a short reaction time. Mechanochemical C-C bond forming reactions gained increasing interest in the past decade. Among those the Knoevenagel condensation is an important reaction for synthezing a,b-unsaturated compounds. The information on the underlying mechanisms of mechanochemical reactions are scarce. In situ investigations using Raman spectroscopy and synchroton XRD either alone or in combination address this challenge. We present the in situ results of a Knoevenagel condensation with p-nitrobenzaldehyde and malononitrile under neat grinding conditions.
In order to investigate their microcracking behaviour, the microstructures of several β-eucryptite ceramics, obtained from glass precursor and cerammed to yield different grain sizes and microcrack densities, were characterized by laboratory and synchrotron x-ray refraction and tomography. Results were compared with those obtained from scanning electron microscopy (SEM). In SEM images, the characterized materials appeared fully dense but computed tomography showed the presence of pore clusters. Uniaxial tensile testing was performed on specimens while strain maps were recorded and analyzed by Digital Image Correlation (DIC). X-ray refraction techniques were applied on specimens before and after tensile testing to measure the amount of the internal specific surface (i.e., area per unit volume). X-ray refraction revealed that (a) the small grain size (SGS) material contained a large specific surface, originating from the grain boundaries and the interfaces of TiO2 precipitates; (b) the medium (MGS) and large grain size (LGS) materials possessed higher amounts of specific surface compared to SGS material due to microcracks, which decreased after tensile loading; (c) the precursor glass had negligible internal surface. The unexpected decrease in the internal surface of MGS and LGS after tensile testing is explained by the presence of compressive regions in the DIC strain maps and further by theoretical arguments. It is suggested that while some microcracks merge via propagation, more close mechanically, thereby explaining the observed X-ray refraction results. The mechanisms proposed would allow the development of a strain hardening route in ceramics.
Gold ist eines der sieben schon im Altertum bekannten Metalle und wurde wg. seines Glanzes und seiner Seltenheit von alters her als Tauschmittel und zur Herstellung von Schmuck benutzt. Außerdem ist es einfach bearbeitbar und weitestgehend gegen chemische Einflüsse resistent. Die Untersuchungen von Gold mit synchrotronstrahlungsangeregter Röntgenfluoreszenzanalyse sind zerstörungsfrei und geben Auskunft über die in der untersuchten Probe vorhandenen chemischen Elemente. Bei den hier vorgestellten Untersuchungen an der BAMline stehen Fragestellungen wie Herkunft, Herstellungsverfahren und Zusammengehörigkeit von Goldfunden im Vordergrund. Die verschiedenen Fragestellungen werden an einer Reihe von Beispielen erläutert die vom Wikingerschatz aus Hiddensee über die Himmelsscheibe von Nebra bis hin zu Funden aus Ägypten langen. Zusätzlich werden die modernen Messmethoden vorgestellt, die am Synchrotron heutzutage zur Verfügung stehen.
Absorption edge tomography, also known as differential tomography at absorption edges, is a method which exploits the sudden change of the attenuation coefficient, when the photon energy crosses the absorption edge of an element. Synchrotron radiation is the best source for absorption edge tomography, because of its small bandwidth, high intensity and easily adjustable photon energy. The synchrotron beamline BAMline at the synchrotron radiation facility BESSY II in Berlin, which is operated by the Bundesanstalt für Materialforschung und -prüfung (BAM), provides a monochromatized beam in a photon energy range from 5 keV up to 80 keV with a bandwidth of 2%, when the double multilayer monochromator is used. Together with the microtomography setup, this enables differential tomography with submicron resolution at the K edge of the elements from chromium up to the lanthanides, and up to uranium, when the L edges are used as well.
In this work, metal organic frameworks (MOFs) embedded in polymer are characterized using differential tomography. MOFs are microporous structures of metal ions, coordinated by organic linker molecules, that can be used in a broad field of applications, especially in gas storage and catalysis. In this work, polymer embedded MOFs were extruded into filaments, which could be used for 3d-printing to profit from the specific properties of the MOFs in polymeric materials combined with the arbitrary shapes provided by 3d-printing. For the extrusion, different polymer classes like ABS, polyester- and polyetherurethanes, as well as different MOFs (ZIF-8, ZIF-67, HKUST-1) were used to create MOF containing filaments with a nominal diameter of 3.0 mm. Differential tomography at the edges of the Zn, Co, and Cu was then used to find the distribution of the corresponding MOF in the filament and to analyze the shape of the inclusions.
XAFS@BAMline
(2018)
X-ray Absorption fine structure spectroscopy (XAFS) is a frequently employed technique in order to investigate structural composition and Change of chemical compounds such as catalytic species or corrosion processes. These structural properties are essential (i) to understand underlying reaction mechanism and (ii) to further improve the design of materials.
While XAFS measurements are usually performed with ionization Chambers or simple fluorescence detectors, we at BAMline specialize in measurements with innovative set-ups that meet Specialrequirements such as time resolution, (3D-) spatial Resolution or demanding sample environments.
This contribution presents various available XAFS configurations with their corresponding applications. In particular, these comprise single -shot XAFS for time- resolved measurements, grazing-exit XAFS with energy and a spatially resolved detector for the characterization of thin films and an in situ grazing incidence Setup for the characterization of corrosion layers.
Additionally,the possibility of analyzing Minute samples in total-reflection geometry is demonstrated.
X-ray absorption fine structure spectroscopy (XAFS) is a frequently employed technique in order to investigate structural composition and change of chemical compounds such as catalytic species. These structural properties are essential (i) to understand underlying reaction mechanism and (ii) to further improve the design of efficient catalysts.
This investigation is based on a newly developed XAFS setup comprising both time- and lateral-resolved XAFS information simultaneously in a single-shot (S2XAFS). The primary broadband beam is generated by a filter/X-ray-mirror combination (bandpass). The transmitted beam through the sample is diffracted by a convexly bent Si (111) crystal, producing a divergent beam. This, in turn, is collected by an area sensitive detector with a theta to 2 theta geometry. This facile, stable and scanningless setup was tested at the BAMline @ BESSY-II (Berlin, Germany).
This contribution focuses on further experimental optimizations allowing the characterization of supported vanadium oxide (VOx) based catalysts at the lower hard X-ray regime (5 to 6 keV). First S2XAFS measurements of these catalysts are presented herein. Supported VOx catalysts show promising results in the oxidation of methane to formaldehyde.
S2XAFS allows determining the structural composition of the metal (i.e. vanadium) based on a fast and smart setup. It is therefore an ideal tool to identify crucial roles of chemical compounds in catalytic reactions.
The Color X-ray Camera CXC or SLcam® is an energy-resolving X-ray camera capable of energy- and space-resolved measurements. It consists of a high-speed CCD detector coupled to a polycapil-lary optic that conducts the X-ray photons from the probe to distinct pixels onto the detector. The camera is capable of fast acquisition of spatially and energy resolved fluorescence images. A dedicated software enables the acquisition and the online processing of the spectral data for all 69696 pixels, leading to a real-time visualization of the elements distribution in a sample. It was developed in a joint project with BAM, IFG Berlin and PN Sensors. In this contribution we will mainly discuss the use of the CXC at our beamline, the BAMline at BESSY II and imaging applications of the CXC from different areas, like biology and archaeometry. Additionally new developments for the use of the detector without optics, like wavelength dispersive detection or 1shot-XANES, will be presented.
We developed a setup for time- and lateral-resolved X-ray absorption fine structure (XAFS) spectroscopy. A dispersive element is placed behind the sample to investigate. The broadband incoming beam transmits the sample, is then dispersed and finally collected by a position sensitive detector. This allows the recording of a whole X-ray absorption near edge structure (XANES) or extended X-ray absorption fine structure (EXAFS) spectrum in a single shot. The dispersive element is a Si(111) crystal, bent by means of a so called wafer bender, developed in house. Our setup is very flexible, easy to adjust and allows a time resolution down to one second which can be used to follow chemical reactions with dynamics on this time scale.
Besides conventional scanning X-ray fluorescence imaging at synchrotron sources, full-field X-ray fluorescence (FF-XRF) imaging techniques that do not implicitly require spatial scanning of the sample have become available. FF-XRF has become achievable thanks to the development of a new type of energy dispersive CCD-based 2D detector, also referred to as a 'color X-ray camera (CXC)' or 'SLcam'. We report on different imaging schemes for biological samples using FF-XRF imaging: (a) 2D 'zoom' imaging with pinhole optics using the 'camera obscura' principle; (b) 2D 'fixed magnification' imaging using magnifying polycapillary optics; and (c) 3D-FF-XRF imaging using an X-ray sheet beam or computed tomography (CT). The different FF-XRF imaging modes are illustrated using the crustacean Daphnia magna, a model organism for investigating the effects of metals on organism/ecosystem health, and foraminifera, a class of amoeboid protist. Detailed analytical characterization of the set-up is performed through analyzing various reference materials in order to determine limits of detection (LODs) and sensitivities. Experiments were performed using the BAMline at the BESSY synchrotron (Berlin, Germany) and using the P06 Hard X-ray Microprobe at the PETRAIII synchrotron (Hamburg, Germany).
Synchrotron radiation sources with their unique properties in terms of intensity, polarization and adjustability offer a wide range of possibilities in materials research. A basic introduction about the creation and special properties of synchrotron radiation will be given. Examples of current work at BAMline, the high-energy measuring facility of the Federal Institute for Materials Research and Testing at the synchrotron BESSY, are used to illustrate the possibilities and limitations of existing measuring methods. It will be shown how the formation of corrosion layers can be tracked, how the abrasion of implants leads to the introduction of heavy metals into the surrounding bone matrix and how the detection of smallest impurities in gold is possible by optimizing the measuring conditions. Finally, an outlook at the hardware and software developments to be expected in the coming years is given.
Bundling analytical capacities to understand phase formation in recycling of functional materials
(2019)
Transitioning from combustion engine-driven transportation to e-mobility demands a paradigm shift – from a system geared to maximize energy efficiency (i.e. fuel consumption) to a system that may be constrained by the availability of high technology (critical) metals required for electrical energy storage systems and drives. In the wake of these developments efforts in securing new resources of these metals from recycling of end-of-life products are increasing steadily.
Recycling of Li-Ion batteries has recently been evaluated. The results pinpoint to a critical need for understanding slag Formation and its dependence on metal components like Mn under extreme conditions. This will allow researchers to predict optimal Operation setting and to react quickly to changing market demands (which may be Li or Co at one point but may also shift to Ni or rare earth elements (REE)). The long-term goal is to control the formation of specific phases in slags allowing for a Maximum yield of elements of interest and optimal recovery in the separation processes that follows. The combination of data on the physical micro structure and local chemistry of the multi-Phase products during and after processing will help to understand and derive thermodynamic and kinetic data on its formation.
In this paper we are giving an overview on the analytical challenges and approaches to provide robust data on local element concentration and species (especially Mn which is a common component of next generation Li-ion batteries cathodes), spanning the dimensions from the nanometer scale to the bulk material. The complementary interactions of X-rays and electrons make them ideal probes to collect Interface and “in-depth” information. Before- and -after studies as well as in situ structural changes and Phase (trans)formation, changes in elemental and elemental species (e.g. oxidation state) distribution may be tracked by X-ray diffraction (XRD), X-ray fluorescence microscopy and X-ray Absorption spectroscopy. The application of such advanced analytical tools will not only provide essential clues during early lab-based experiments towards the development of new recycling technologies, but may also be deployed for on-line and in-line monitoring of industrial processes.
In X-ray fluorescence (XRF), a sample is excited with X-rays, and the resulting characteristic radiation is detected to detect elements quantitatively and qualitatively. Quantification is traditionally done in several steps:
1. Normalization of the data
2. Determination of the existing elements
3. Fit of the measured spectrum
4. Calculation of concentrations with fundamental parameters / MC simulations / standard based
The problem with standard based procedures is the availability of corresponding standards. The problem with the calculations is that the measured intensities for XRF measurements are matrix-dependent. Calculations must, therefore, be performed iteratively (= time consuming) in order to determine the chemical composition.
First experiments with gold samples have shown the feasibility of machine learning based quantification in principle. A large number of compositions were simulated (> 10000) and analyzed with a deep learning network. For first experiments, an ANN (Artificial Neural Network) with 3 hidden layers and 33x33x33 neurons was used. This network learned the mapping of spectra to concentrations using supervised learning by multidimensional regression. The input layer was formed by the normalized spectrum, and the output layer directly yielded the searched values. The applicability for real samples was shown by measurements on certified reference materials.